Fire Safety Journal 46 (2011) 451–461

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Fire Safety Journal

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Characterization of thermal properties and analysis of combustion behavior

of PMMA in a cone calorimeter
Jocelyn Luche a,n, Thomas Rogaume a, Franck Richard a, Eric Guillaume b
a
Institut Pprime, UPR 3346 CNRS, Département Fluides, Thermique, Combustion, ENSMA, BP 40109, 86961 Futuroscope, France
b
Laboratoire national de métrologie et d’essais (LNE), Test Direction, 78197 Trappes Cedex, France

a r t i c l e i n f o abstract

Article history: This paper deals with the thermal degradation of a black poly(methyl)methacrylate (PMMA) in a cone
Received 10 January 2011 calorimeter (CC) in air with a piloted ignition. The influence of several heat fluxes (11 kW m  2 and
Received in revised form 12 kW m  2, and ten values from 15 to 60 kW m  2 in steps of 5 kW m  2) on PMMA sample degradation
14 July 2011
and the decomposition chemistry has been studied. Thus, thermal properties have been deduced and
Accepted 18 July 2011
calculated from ignition time and mass loss rate (MLR) curves. During our experiments, among
Available online 9 August 2011
compounds quantified simultaneously by a Fourier transformed infrared (FTIR) or gas analyzer, five
Keywords: main species (CO2, CO, H2O, NO and O2) have been encountered, regardless of the external heat flux
PMMA considered. The main product concentrations allow calculation of the corresponding emission yields.
Cone calorimeter
Thus, mass balances of C and H atoms contained in these exhaust gases were able to be compared with
FTIR
those included in the initial PMMA sample. Using the standard oxygen consumption method, heat
Heat release rate
Mass loss rate release rate (HRR), total heat release (THR) and effective heat of combustion (EHC) have been calculated
Emission yields for each irradiance level. Therefore, these different results (thermal properties, emission yields, HRR,
Effective heat of combustion THR and EHC) are in quite good accordance (same order of magnitude) with those found in previous
Thermal properties studies.
ISO 5660 standard & 2011 Elsevier Ltd. All rights reserved.

1. Introduction
Plastics and polymers, such as poly(methyl)methacrylate
(PMMA), are used as replacements for conventional materials
(e.g. wood, metals, glass, etc.) in numerous domains such as
electrical appliances, light diffusers, optical fibers, furniture,
transport, hygiene and health, etc. Indeed, these widespread kinds
of synthetic compounds, with good technical, mechanical, chemi-
cal, optical performances, etc., are easily manufactured for a
moderate cost and can be used in a wide range of applications.
Thus, compounds made of PMMA can be used in numerous
applications as signs and signboards (illuminated panels, 3D
lettering, indicator panels, etc.), POS (point-of-sale) advertising
(display stands, testers, notice-boards, etc.), interior design (shop-
fitting, furniture, projection screens, glazing, etc.), transport
(deflectors, sun visors, registration plates, ship portholes and
windows, etc.) or industrial (machine guards, dials, precision
parts, etc.) devices. In spite of these various uses linked to
numerous advantages, plastics (highly combustible materials)
constitute a grave danger (human injuries and deaths) in case of
n
Corresponding author.
E-mail address: jocelyn.luche@lcd.ensma.fr (J. Luche).
fire, as under the right conditions, they readily ignite and burn
vigorously.
As a reference fuel material used in a cone calorimeter (CC),
solid acrylic PMMA polymer has been widely used – with or
without filler – during previous studies for assessing polymer
flammability and characterizing the mass loss rate (MLR) during
combustion processes [1–14]. Only some of these previous
studies and other specific studies propose the chemical analysis
and quantification of the effluents emitted during PMMA thermal
degradation, and so include the calculation of the heat release
rate (HRR), which is the most important parameter in fire
characterization studies [1–5,15–22]. Finally, a few studies pro-
pose a chemical kinetic mechanism for predicting the PMMA
degradation in a CC [23,24]. Generally, only the assumption of a
single-step degradation corresponding to depolymerization and
formation of MMA is carried out.
The present paper deals with a complete and detailed study of
thermal degradation of a black non-charring PMMA in a CC,
including the characterization of thermal properties and the
quantification of exhaust gas concentrations of this typical poly-
mer. Thus, the main purpose of this work is to characterize the
influence of a widespread range of irradiance levels (external heat
flux) on the MLR of a PMMA sample and on the product amounts
released during this combustion process. Next, the HRR was
determined based on the O2-consumption principle in a CC.

0379-7112/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.firesaf.2011.07.005
452 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461

Nomenclature HRR averaged heat release rate, kW m  2

k thermal conductivity, kW m  1 K  1
Greek notations
m mass, g
MAir molar mass of air, g mol  1
e emissivity m_ Air mass flow rate of the incoming air, g s  1
f oxygen depletion factor Mi molar mass of species i, g mol  1
krc thermal effusivity, kJ2 m  4 K  2 s  1 m_i mass flow rate of species i in the exhaust duct of CC,
r density, kg m  3 g s1
s Stefan–Boltzmann constant 5.6704  10  8 W m  2 K  4 m_e mass flow rate in the exhaust duct of CC, g s  1
MLR mass loss rate, g s  1
Notations NDIR non-dispersive infrared, –
P pressure, Pa
A sample area exposed to cone calorimeter heat flux, PMMA poly(methyl)methacrylate, –
cm2 q_ 00ext external heat flux, kW m  2
c specific heat, kJ kg  1 K  1 R universal constant of perfect gas
CC cone calorimeter, – 8.314472 J mol  1 K  1
CHF critical heat flux, kW m  2 SMLR s mass loss rate, g m  2 s  1
DHg latent heat of gasification, kJ g  1 SMLR averaged specific mass loss rate, g m  2 s  1
E net heat release per unit mass of oxygen consumed, t time, min or s
MJ kg  1 of O2 T temperature, K
ECO net heat release per unit mass of oxygen for CO, tig ignition time, min or s
MJ kg  1 of O2 Tig ignition temperature, K
EHC effective heat of combustion, kJ g  1 T0 initial (ambient) temperature, K
EHC averaged effective heat of combustion, kJ g  1 THR total heat release, MJ m  2
FHF flame heat flux, kW m  2 V_ e volumetric flow rate in the exhaust duct, L s  1
FHFnet net flame heat flux, kW m  2 Vm molar volume, L mol  1
FID flame ionization detector, – Xi0 mole fraction of species i in the incoming air, –
FTIR Fourier transformed infrared, – Xi mole fraction of species i in the exhaust gas measured
hc convective heat transfer coefficient, W m  2 K  1 by analyzer, –
HRR heat release rate, kW m  2 Yi emission yield of species i, gi/gsample

Finally, the MLR and HRR parameters have been correlated with Elementary analysis results show that no inert load, flame
main gaseous compound evolutions and their emission yields to retardants or fillers were used during the manufacturing of the
propose a description of physical and chemical phenomena PMMA sample; neither chlorine- nor sulfur-based additives were
occurring during PMMA thermal degradation. found. Indeed, 100 wt% of the total sample mass was composed of
C, H, O, N and S atoms. This result is in good accordance with
various compositions of such PMMA reported in [25]. Based on
this elementary analysis composition, the raw chemical formula
2. Experiments of the virgin PMMA was determined to be (C4.9H7.8O2.0)n (with
n¼PMMA polymerization degree).
2.1. Materials Its molecular weights and molecular weight distributions were
obtained from an Agilent Technologies Size Exclusion Chromato-
The material used in this study is a black non-charring PMMA, graphy (SEC) calibrated with a polystyrene standard. Samples of
commonly known as Altuglas, supplied by the company VACOUR 25 and 70 mg (1 and 2 in Table 2) were dissolved in chloroform
and synthesized via radical polymerization. The PMMA elemen- and then injected into the SEC. Table 2 shows the molecular
tary analysis was conducted by a combination of catharometry weights (Mn and Mw), molecular weight distributions (Ip) and
and non-dispersive infrared (NDIR) detection. Table 1 presents the polymerization degree (n) of each sample analyzed.
averaged composition along with the analysis methods that were Molecular weight distribution (Ip), with a value around 3.7,
repeated three times and provided a dispersion of 70.3 wt%. shows that PMMA is a polymolecular compound obtained by
radical polymerization (IpZ2) according to the definition given
Table 1 by some authors in the literature [26,27]. From these results, the
Elemental analysis of black poly(methyl
methacrylate).
polymerization degree (n) of the PMMA sample can be deter-
mined as equal to value ranging from 1500 to 1800.
Elements Composition (wt%)

Carbon (C) 59.1

Hydrogen (H) 7.9 Table 2
Oxygen (O) 31.9 Characterization of black poly(methyl)methacrylate mass (SEC analysis).
Nitrogen (N) o0.3
Sulfur (S) o0.2 Elements Mn Mw Ip¼ Mw/Mn n
Chlorine (Cl) 0.1
Water (H2O) 0.6 1 178,670 639,340 3.6 1785
Total o100.1 2 150,440 578,480 3.8 1503
 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461 453

2.2. Cone calorimeter HORIBA apparatus during our experiments. Moreover, this
FTIR spectrometer allows the identification and quantification
The PMMA reaction-to-fire characterization was carried out in of other combustion products such as NO2, NH3, HCN, N2O,
a CC (Standard ISO 5 660 [28]) made by Fire Testing Technology CH4, C2H2, C2H4, C2H6, C3H6, C3H8 and H2O (not quantified by
Limited, under fully ventilated conditions. The sample dimensions the HORIBA gas analyzer).
were 99 71 mm long, 9971 mm wide and 14 71 mm thickness,
with a mass of 169.6 72.9 g. Thus, mass density (r) calculated
Furthermore, before all the experiments, the two devices used
from these data is found to be equal to 1213.3719.1 kg/m3. Fig. 1
for gas analysis were calibrated with well-known concentration
presents a schematic view of the CC with a solid PMMA matrix in
standards to quantify the five gaseous combustion products for
the sample holder exposed to an irradiance level from an electric
the HORIBA apparatus and the 15 products for the FTIR spectro-
heater. Several heat flux levels were used: 11 and 12 kW m-2, and
meter measured simultaneously during the combustion process.
ten heat flux levels from 15 to 60 kW m-2 in steps of 5 kW m-2.
The entire transport line (from the sampling point to the
Tests were carried out with a piloted ignition in air, and were
quantification apparatus) was heated to 170 1C and was not dried
repeated at least five times for each condition. Moreover, the
before passing through the FTIR measurement gas cell. This
ignition spark was positioned above the sample up to ignition
allowed the transport of combustion products while avoiding
(and removed thereafter), so all the tests were performed in a
water vapor condensation and the trapping of water-soluble
flaming condition. According to the standard ISO 17554 [29], the
compounds. It also enabled quantification of H2O (vapor).The
experiments were stopped manually if no ignition occurred after
sampling line was connected to a filtration box where a cellulosic
30 or 32 min after ignition or when the mass loss became zero.
filter and a stainless steel filter were used to retain heavy
During these experiments, the CC fan flow rate was taken to be
products and soot particles. After filtration, gases were trans-
equal to 0.024 70.002 m3 s-1. At the end of all experiments and,
ported up to the gas analyzers (FTIR and HORIBA). The FTIR
regardless of the external heat flux chosen, all the PMMA sample
analysis technique used (including sampling and filtering device)
was entirely degraded, and no solid or liquid residue was found
was validated during the SAFIR project [30], which constituted
inside the sample holder.
the basis for toxicity analysis carried out following the guidelines
of the standard ISO 19702 [31–35].
2.3. Gas analysis

Exhaust gases produced by the thermal degradation of the

PMMA sample in the CC were sampled from the exhaust duct 3. Thermal property results
using two kinds of on-line gas analyzers:
3.1. Parameters of inflammation and combustibility
 A gas analyzer HORIBA PG 250 equipped with three units to
simultaneously quantify gaseous products (NO, O2, CO2, CO For the PMMA studied in the CC under the conditions outlined
and SO2). The NOx analysis unit uses a cross-modulation in the previous part, sample ignition can be achieved when an
ordinary pressure chemiluminescence method, the SO2, CO, external heat flux q_ 00ext (with a relative uncertainty of 75%), higher
and CO2 unit uses an NDIR absorption method and the O2 unit than a critical heat flux (CHF), is applied during a time interval tig .
uses an electrochemical Zirconia method using a galvanized These different parameters can be defined and calculated by using
cell. The sampling flow rate was 0.4 NL min  1. Eqs. 1 and 2, which are described and fully detailed in Refs.
 A Fourier transformed infrared (FTIR) spectrometer (Thermo- [1–4,14]:
Nicolet 6700 equipped with a MCT-A detector and a measure-  
ment gas cell of volume¼0.2 L and optical path-length¼2 m). 2 Tig T0 2
tig ¼ krc 00 ð1Þ
The sampling flow rate was equal to 2 NL min  1. The FTIR 3 q_ ext
analyzer was also used to quantify the NO, CO2, CO and SO2
species, which allows the control and comparison of these 1h i
q_ 00ext ¼ hc ðTig T0 Þ þ esTig4  CHF ð2Þ
concentration values with those values measured using the e

Cone calorimeter fan

Spark ignition

Temperature and differential

pressure measurements

Cone calorimeter hood Soot filter

GAS ANALYZERS:
-FTIR
-HORIBA PG250

Heated sampling line (170°C)

Cone calorimeter (Electrical heater)

Weighting Sample holder

device

Fig. 1. Schematic layout of the coupling of cone calorimeter and gas analyzers.
454 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461
" # " #
1 e 00
hc ðTig T0 Þ þ esTig4
pffiffiffiffiffi ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi _
Uq ext  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
tig ð2=3ÞkrcðTig T0 Þ ð2=3ÞkrcðTig T0 Þ
1=2
The slope of a plot obtained from the tig ¼ f ðq_ 00ext Þ curve
(Eq. (3)) allows computation of the different thermal properties
such as the theoretical critical heat flux (CHF), the specific heat
(c), the thermal conductivity (k) and the theoretical ignition
temperature (Tig) by using the following equations:
" # " #
4
e hc ðTig T0 Þ þ esTig
Slope ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ; yintercept ¼  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ð2=3ÞkrcðTig T0 Þ ð2=3ÞkrcðTig T0 Þ
 
yintercept
CHF ¼ 
Slope
Fig. 2 shows plots of the curve evolution of the square root of
the inverse of ignition time as a linear function of external
irradiance (Eq. (3)), with a straight line used to fit the data
(slope¼0.00509 and yintercept ¼  0.02434) up to the minimum
experimental heat flux corresponding to critical ignition
(11 kW m  2) represented by a vertical dashed line. Moreover, in
Fig. 2, the fit line (the curve slope) reaches an intersection point
with the x-axis of approximately 4.8 kW m  2. This value repre-
sents the theoretical CHF for PMMA ignition computed from
Eqs. (4) and (5). This CHF theoretical result is in good accordance
with previous results found in the literature where the CHF
(obtained by the same way) is equal to 4 kW m  2 [11] or
5 kW m  2 [1–5]. The effective CHF determined experimentally
in this study (11 kW m  2) is in good accordance with results
found in the literature (9–13 kW m  2 [5,11,14,36]).
The difference between the experimental and extrapolated CHF
is due to the non-linearity of the ignition time leading to the
non-linearity of the square root of the inverse of ignition time
(Fig. 2) for the lowest external heat flux, especially near the
CHF [14] (where the solid material is thermally thin compared
to the time of thermal transfer). Another explanation [5] of this
Fig. 2. Square root of the inverse of ignition time (s  0.5) as a function of heat flux
(kW m  2).
difference between theoretical and experimental values of CHF
ð3Þ has suggested the influence of the surface reradiation of the
PMMA sample, which causes a higher experimental CHF than
the value extrapolated from Fig. 2. Moreover, different methods
described in previous studies [37–39] have shown that the
theoretical CHF value can be used to calculate a more realistic
CHF. Indeed, for example, some intercept values (CHF) are defined
by the authors as being only 0.64 [37] or 0.76 [38] fraction of
the CHF.
3.2. Transient burning rate
ð4Þ
Fig. 3 shows the experimental transient evolution of the MLR
ð5Þ at the different external irradiance levels or external heat flux
used during the PMMA thermal degradation experiments. Time
t¼0 marks the beginning of the exposure to the desired irra-
diance level rather than the moment of ignition.
Regardless of the heat flux chosen, three or four – more or less
significant – decomposition time ranges (corresponding to three
or four peaks or slope variations, which reach a maximum MLR
value as summarized in Table 3) can be observed in Fig. 3 with a
major one that has the most significant peak intensity (corre-
sponding to the 3rd stage in Table 3). Moreover, an increase of
external heat flux moves the different stages towards the first one
while increasing curve intensity. Indeed, when the external heat
flux increases from 11 to 60 kW m  2, all the PMMA sample mass
is lost on a shorter time (e.g. around 10 min at 60 kW m  2 against
45 min at 11 kW m  2), with a higher maximal intensity of the
MLR peak (e.g. around 0.5 g s  1 at 60 kW m  2 compared to
0.15 g s  1 at 11 kW m  2). As shown, the MLR shapes and their
intensities depend strongly on and change with the irradiance
level value. After a latency time, the first stage starts with the
ignition of the PMMA sample and the very quick rise of MLR after
ignition. Next, the PMMA decomposition continues during the
2nd and 3rd time ranges, which correspond to the MLR evolution
following a plateau (2nd column of Table 3) and reach a
significant peak (3rd column of Table 3), respectively. Finally,
the last decomposition time range (4th column of Table 3)
corresponds to an MLR decrease and the consumption of the
remaining PMMA amount in the sample holder. At the end of the
different experiments, no liquid or solid residue was found in the
sample holder.
The specific mass loss rate (SMLR) is determined as the ratio
between the MLR and the sample surface exposed to the CC
external irradiance level (i.e. A¼88.4 cm2, as explained in the
paragraph 6.7 of the ISO 5660 standard [28], where the opening
for the specimen face exposed to heat flux coming from the CC
heater is equal to 9.470.5 cm  9.470.5 cm). Moreover, the
SMLR is defined (Eq. (6)) as the sum of the heat flux from the
flame (FHF) and the external heat flux (q_ 00ext ), less the radiative
heat flux loss (esTig4 ), divided by the latent heat of gasification
(DHg ). According to a hypothesis carried out in previous studies
[1–4], black PMMA approximates a vaporizing solid, and the
flame heat flux (FHF) is constant. The FHF [1–4] or total
FHF [9] is defined as the sum of the radiative (FHFr) and
convective (FHFc) components of the FHF (FHF ¼ e FHFr þFHFc ,
where e is emissivity). The net FHF [1–4,9] is defined as the
material’s contribution to burning in the CC and is the difference
between (total) FHF and radiative heat flux loss from the sample
surface (FHFnet ¼ FHFesTig4 ).
  4
1 FHFesTig
SMLR ¼ q_ 00ext þ ð6Þ
DHg DHg
Experimental averaged SMLRs are plotted in Fig. 4 as functions
of external incident heat flux. The SMLR (or MLR) is accelerated
 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461 455

Table 3
Time range of the four stages of PMMA thermal degradation.

Time range (min)

Heat flux (kW m  2) 1st stage 2nd stage 3rd stage 4th stage

11 23  25 25  35 35  45 445
12 13  15 15  24 24  34 434
15 57 7  15 15  25 425
20 23 3  12 12  18 418
25 12 29 9  15 415
30 0.5  1.5 1.5  8 8  14 414
35 0.5  1 18 8  11.5 411.5
40 0.5  1 1  7.5 7.5  10.5 410.5
45 0.2  0.4 0.4  7 7  10 410
50 0.2  0.4 0.4  6.5 6.5  9 49
55 0.2  0.4 0.4  5 5  8.5 48.5
60 0.2  0.4 0.4  5 58 48

Fig. 4. Averaged specific mass loss rate SMLR (g m  2 s  1) vs. heat flux (kW m  2).

The slope ( ¼0.4268) and yintercept ( ¼6.3606) of the best fit line

to flaming black PMMA data obtained from the SMLR ¼ f ðq_ 00ext Þ
curve (Eq. (6)) allows the computation of other thermal properties
such as gasification heat (DHg ¼2.34 kJ g  1), flame heat flux
(FHF¼17.67 kW m  2) and net flame heat flux (FHFnet ¼
14.90 kW m  2) by using Eq. (7), which is deduced from Eq. (6):

1 FHFesTig4
Slope ¼ ; yintercept ¼ ð7Þ
DHg DHg

The black PMMA gasification heat (DHg ¼2.34 kJ g  1) found in

Fig. 3. Mass loss rate (g s  1) as a function of experimental time (min).
when the irradiance level is increased up to a high value. Indeed,
the SMLR increases from 11 to 32 g m  2 s  1 when incident heat
flux increases from 11 to 60 kW m  2.
this study is in good accordance with previous results from the
literature, as presented in Table 4.
As seen for thermal properties and CHF, theoretical results
calculated or experimental ones measured during this black
PMMA thermal degradation study in a CC are of the same
magnitude order as those found previously in literature. Slight
differences can be observed between the different results; this is
probably due to the wide disparity between PMMA samples used,
indicating a real difference due to elementary composition and
456 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461

density as well as experimental measurement uncertainties. The
difference between results can also be explained by the difference
due to the cone designs used or due to result interpretations. In
the latter case, in the literature for theoretical CHF determination,
only a part of the results (up to 40 kW m  2 in [1–4] or between
20 and 50 kW m  2 in [5]) are fitted by a straight line, which has a
more or less significant influence on the CHF determination, and
so influences the computation of other parameters (c, k, DHg).
3.3. Heat release rate (HRR)
The HRR is the most significant parameter for the fire hazard
material evaluation [40,41] since it controls the rate of growth in
fire, including heat and ultimately the amount of smoke and toxic
gas generated. This parameter is measured by using the oxygen
consumption calorimetry technique [42] based on the ISO 5660
standard [28]. The O2, CO2, CO, H2O and N2 species account for
approximately 99% of the exhaust gases in the majority of full-
scale fire tests [43,44]. Thus, these gaseous compounds, identified
as the major species in our experimental results (Fig. 7 and
Table 5), will be considered as the only species in the exhaust
gas flow. As H2O concentrations were measured during our
experiments, the HRR value can be computed by the following
equations (described in detail in Refs. [43–49]):
 
1 1f XCO MO2
HRR ¼ EfðECO EÞ _ ð1XH0 O XCO
m 0
ÞXO0 2 ð8Þ
A 2 XO2 MAir Air 2 2
Me ¼ 18 þ 4ð1XH2 O ÞðXO2 þ 4XcO2 þ 2:5Þ ð11Þ
where A¼88.4 cm2 (sample area exposed to CC heat flux),
1
E¼13.1 MJ kg  1 of O2; ECO ¼17.6 MJ kg  1 of O2; MO2 ¼ 32 g mol ,
MAir ¼29 g mol  1, m_ Air is the mass flow rate of the incoming air, m
_e
is the mass flow rate in the exhaust duct of the CC, Xi is the mole
fraction of species i in the exhaust gas measured by the analyzer, Xi0
is the mole fraction of species i in the incoming air and f is the
oxygen factor.
Fig. 5 shows the transient evolution of the SMLR and the HRR
at four irradiance levels (15, 30, 45 and 60 kW m  2). As seen
previously for MLR, HRR and SMLR in this paper, transient
evolutions of these parameters depend strongly on the irradiance
level, and both parameters have the same curve shapes compared
to the MLR one for a given external heat flux. As for the MLR
transient evolution in Fig. 3, the four PMMA thermal decomposi-
tion stages summarized in Table 3 are also found from HRR and
SMLR curves in Fig. 5, regardless of the incident heat flux applied
to the sample.

XO0 2 ð1XCO XCO2 ÞXO2 ð1XCO

0
Þ
f¼ 2
ð9Þ
XO0 2 ð1XO2 XCO XCO2 Þ

_ Air
m _e
ð1XH2 O Þð1XO2 XCO XCO2 Þ m
¼ ð10Þ
MAir ð1XH0 2 O Þð1XO0 2 XCO
0 Þ
2
Me

Table 4
Comparison of PMMA gasification heat of this
study with values from literature.

DHg (kJ g  1) References

2.34 This study

1.34–1.48 [12]
1.6 [5,6,10,11–13]
1.96 [8]
2.2–2.7 [6]
2.6 [9]
2.77 [1–4]
Fig. 5. HRR and SMLR curves as functions of time at different external heat flux.

Table 5
HRR, SMLR , EHC and THR obtained during this study and from literature.

Results from this work Results from literature

2 2
Heat flux (kW m ) HRR (kW m 2
) SMLR (g m 2
s 1
) EHC (kJ g 1
) THR (MJ m ) HRR (kW m)  2 EHC (kJ g  1)

11 274.3 7 116.1 11.2 74.5 24.0 72.3 445.6

15 317.4 7 111.1 12.8 74.4 25.0 73.0 450.1 21.8 [23]
20 349.4 7 138.5 15.0 75.3 23.7 76.7 452.9
25 412.0 7 166.0 17.4 76.3 24.0 76.2 450.4 401.56 [1–4] 24.0 [1–4]
30 463.8 7 222.0 18.6 77.9 24.8 74.0 466.4
35 499.9 7 238.7 20.8 79.0 24.7 79.1 451.1 23.2 [15,16]
40 577.7 7 267.4 23.2 79.9 24.9 72.3 466.4
45 633.4 7 303.4 25.9 710.5 24.0 74.1 471.1
50 691.4 7 346.9 27.7 711.4 24.6 74.4 492.6 642.21 [1–4] 24.1 [1–4]
55 735.3 7 315.4 30.5 712.2 25.3 77.7 459.4
60 780.8 7 365.7 31.6 713.0 24.3 72.8 468.5
Mean 521.4 7 174.8 21.3 77.0 24.5 70.5 461.3 7 13.6 24–25
[5,14,17–21,45]
 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461
The effective heat of combustion (EHC) value is a time- and
irradiance-level-dependent parameter that corresponds to the
heat released from the volatile portion during solid material
combustion. From the HRR and SMLR, the EHC can be computed
using the following equation:
HRR
EHC ¼ ð12Þ
SMLR
Averaged results for SMLR, HRR, EHC and total heat release (THR)
are presented in Table 5 for the set of irradiance levels studied (from
11 to 60 kW m  2). Globally, HRR increases from 275 to 780 kW m  2,
SMLR increases from 11 to 32 g m  2 s  1, EHC values are around to
24.570.5 kJ g  1 and THR values are around 460714 MJ m  2 with
increasing external heat flux (from 11 to 60 kW m  2, respectively).
These averaged HRR and/or EHC results are compared to some black
PMMA thermal degradation data found in the literature. As seen in
Table 5, results found during this black PMMA thermal degradation
study in the CC are in quite good accordance (same order of
magnitude) with those given by previous studies.
4. Exhaust gas concentrations and emission yields
In Fig. 6, CO2 concentrations obtained simultaneously from the
gas analyzer (HORIBA) and the FTIR spectrometer are plotted as
functions of time for external heat fluxes equal to 15, 30, 45 and
60 kW m  2. As can be seen in Fig. 6, regardless of the heat flux
considered, good accordance is observed between the CO2
concentrations measured with the two types of gas analysis
devices. The same observations can be carried out for the CO and
NO concentration comparison between the HORIBA gas analyzer
and the FTIR spectrometer. Therefore, regardless of the CO or CO2
concentrations chosen (measured with the HORIBA or the FTIR
apparatus), this choice has a minor impact (o2%) on the different
calculation results, i.e. on HRR, EHC, THR or emission yield results.
External heat flux influence on PMMA sample thermal degra-
dation has been studied with concentration evolution of major
products. Evolution curves of CO, CO2, O2, H2O, NO, NO2 and HCN
concentrations are plotted as functions of time for an external
Fig. 6. Comparison of CO2 concentrations (ppm) from gas analyzer and FTIR as
functions of time (min) at 15, 30, 45 and 60 kW m  2.
457
heat flux equal to 15, 30, 45 and 60 kW m  2 (Fig. 7a–d, respec-
tively). As can be seen in Fig. 7, an influence of the external heat
flux value can be noticed between the different curve sets for each
exhaust gas. Indeed, when the irradiance level increases from 11
to 60 kW m-2, CO, CO2, H2O, NO, NO2 and HCN concentration
levels increase, and the O2 one decreases.
During these experiments, concentrations of CH4, C2H2, C2H4,
C2H6, C3H6 and C3H8 have been measured with maximum values
that never exceed 10 ppm. No significant amounts ( o1 ppm) of
SO2, N2O or NH3 have been quantified (i.e. the maximum value
measured for each concentration is near the detection limit, but
lower than the quantification limit of the gas analysis apparatus
for these gaseous compounds).
Moreover, curve evolutions of main exhaust gas production
(and thus O2 consumption) are linked to the MLR curve evolution.
Indeed, when the PMMA sample is degraded (i.e. MLR increases),
we can observe an oxygen consumption (O2 concentration
decreases) and simultaneously an exhaust gas production
(concentrations of volatile gases, such as CO, CO2, H2O, NO, NO2
and HCN, increase). Conversely, when the PMMA thermal degrada-
tion becomes less important (i.e. MLR decreases), O2 amount rises
(i.e. reaches the initial ambient value of O2 concentration) and
other major product concentrations decrease. Thus, the curve
shapes of these different products (and the oxygen one by the
mirror effect) correspond perfectly to the MLR ones. So, the
physical and the chemical events arising during the PMMA thermal
degradation process can be identified by correlating the MLR and
gaseous compound curves with Table 3 given in Section 3.
The product emission yields quantified during the different
experiments are useful tools to extrapolate exhaust gaseous
species production obtained from bench-scale (CC) to full-scale
scenarios [42]. Table 6 gives the emission yields of the main
products released during the PMMA decomposition process. The
gaseous species emission yields (Yi), calculated as the ratio
between the exhaust product i mass flow rate (m _ i ) and the PMMA
MLR, are expressed by the following equation:
m_i
Yi ¼ ð13Þ
MLR
The mass flow rate of species i released during the combustion
process (Eq. (14)) is represented by the product of the species
mole fraction (Xi), the volumetric flow rate in the exhaust duct
(V_ e ), the molar mass of species i (Mi) divided by the molar volume
(Vm) given by Eq. (15), where R is the universal constant of a
perfect gas, and T and P are the temperature and the pressure of
the gas mixture in the CC exhaust duct, respectively;
Xi V_ e Mi
_i¼
m ð14Þ
Vm
RT
Vm ¼ ð15Þ
P
During the burning process, only three species (CO, CO2 and
H2O) present emission yields of high consistency. Emission yields
of these species are found to be quite constant (taking into
account uncertainties on measurements and calculations), regard-
less of the initial irradiance level used during the experiments.
Indeed, in Table 6, CO and H2O emission yields decrease slightly
from 0.008 to 0.006 gCO/gsample for CO and from 0.7 to 0:6 gH2 O =g
for H2O when the irradiance level increases from 11 to
60 kW m  2, respectively. Conversely, CO2 emission yields
increase slightly from 2.0 to 2:2 gCO2 =g when the external heat
flux increases from 11 to 60 kW m  2, respectively. Moreover, for
the irradiance level range studied (from 11 to 60 kW m  2), mean
values are found to be equal to 0.007 gCO/gsample, 2:148 gCO2 =g
and 0:658 gH2 O =g . Other chemical compounds (e.g. NOx, HCN or
458 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461

Fig. 7. Major product concentrations (ppm) and mass loss rate (g s  1) as functions of time (min) at 15 (a), 30 (b), 45 (c) and 60 kW m  2 (d).

Table 6
Emission yields of main exhaust products released during PMMA combustion.

External heat Chemical compound yields (gspecies/gsample) CO/CO2 (%)

flux (kW m  2)
CO CO2 H2O

11 0.008 70.001 2.034 70.407 0.720 7 0.144 0.362

12 0.008 70.002 1.977 7 0.395 0.758 7 0.152 0.383
15 0.008 70.002 2.126 7 0.425 0.748 7 0.150 0.380
20 0.008 70.002 2.169 7 0.434 0.694 7 0.139 0.361
25 0.006 70.001 2.069 70.414 0.655 7 0.131 0.309
30 0.006 70.001 2.160 70.432 0.633 7 0.127 0.293
35 0.006 70.001 2.182 7 0.436 0.640 7 0.128 0.275
40 0.006 70.001 2.206 70.441 0.582 7 0.116 0.266
45 0.006 70.001 2.216 7 0.443 0.649 7 0.130 0.262
50 0.006 70.001 2.217 7 0.443 0.611 7 0.122 0.250
55 0.006 70.001 2.201 70.440 0.614 7 0.123 0.262
60 0.006 70.001 2.221 7 0.444 0.587 7 0.117 0.257
Mean 0.007 70.001 2.148 7 0.430 0.658 7 0.132 0.305

light hydrocarbons), which have been measured during these 5. Discussion

experiments, have low emission yield values (i.e. o1 m g/gsample),
regardless of the irradiance level considered.
During this study in a CC, the averaged emission yield results
found for CO2 and CO species (i.e. 2:148 gCO2 =gPMMA and
0.007 gCO/gPMMA) are comparable with those found in previous
studies [1–4] (i.e.  2:54 gCO2 =gPMMA and  0.008 gCO/gPMMA),
[14] (i.e.  2:12 gCO2 =gPMMA and  0.010 gCO/gPMMA), [15,16]
(i.e.  3:23 gCO2 =gPMMA and  0.016 gCO/gPMMA) or [40–42]
(i.e.  2:05 gCO2 =gPMMA and  0.010 gCO/gPMMA).
The thermal degradation study of virgin PMMA has allowed the
computation of several thermal properties (Section 3), of this
polymer, which are in good accordance with previous studies:
theoretical CHF 5 kW m  2, experimental CHF¼ 11 kW m  2,
DHg ¼2.34 kJ g  1, averaged heat release rate HRR  275–780
kW m  2 for external heat fluxes ranging from 11 to 60 kW m  2,
respectively, and EHC 24.5 kJ g  1, regardless of the external heat
flux chosen.
 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461 459

The chemical analysis (Section 4) of the exhaust gases
by FTIR, NDIR and flame ionization detection (FID) has shown
that only four products (CO, CO2, H2O and NO) and O2 were
measured as main species. Indeed, low concentrations were
measured for the other compounds, such as NO2, light hydro-
carbons and HCN. Emission yields of all species quantified during
this work have been calculated and only CO, CO2, H2O, NO and O2
have values of high consistency (i.e. higher than 1 mg/gsample).
This was confirmed by the atomic balances for C and H presented
in Table 7, which compares the C and H atom masses contained in
the initial PMMA and those contained in the main gaseous
products (i.e. CO, CO2 and H2O). Indeed, C atom masses from
CO and CO2, and H atom masses from H2O are, in the majority
of cases (taking into account measurement uncertainties),
equal to the initial C and H atom masses of the PMMA sample,
respectively.
The results in Table 7 show that all initial C and H amounts
(taking into account measurement uncertainties) are converted
into H2O, CO and CO2 species, and no other compound (or in very
small amounts, i.e. o1 mg/gsample, as measured for light hydro-
carbons or HCN) containing high quantities of C and/or H atoms
(e.g. heavy hydrocarbons, polycyclic aromatic hydrocarbons, soot,
etc.) seems to be produced during thermal degradation of PMMA.
Thus, the same amount of exhaust gas (i.e. the same value of
exhaust gas emission yield) is produced during the thermal
degradation process, regardless of the external heat flux applied
to the PMMA sample (no residue found in the sample holder at
the end of the different experiments). However, the MLR or HRR
correlated with species concentration evolutions have shown that
external heat flux has an influence on the intensities of sample
degradation (transient MLR curves) or product emission/con-
sumption (transient HRR and concentration curves). Indeed, when
external heat flux increases from 11 to 60 kW m  2, the SMLR
increases from 11 to 32 g s  1 m  2 and the HRR increases from
275 to 780 kW m  2, respectively. Moreover, external heat flux
has an influence on thermal degradation and product evolution
durations, which are faster for higher external heat (  10 min at
60 kW m  2 vs.  45 min at 11 kW m  2).
As seen previously (Sections 3.3), in our experimental conditions
in the CC, the PMMA sample thermal decomposition seems to take
place according to four time ranges – more and less significant and
separated, depending on incident heat flux – which are deduced from
Fig. 3 and summarized in Table 3. From transient evolutions of the
main released product concentrations, MLRs and HRRs, the four main
time ranges where thermal decomposition of black PMMA takes
place and the associated physical and chemical phenomena can be
identified as follows:
– A first one (1st column in Table 3) corresponding to the start of
thermal degradation with the beginning of ignition. During
this first time range, a significant bubbling phenomenon at the
PMMA sample surface occurred, and all concentrations (except
for the O2 one, which decreased) and MLR increased strongly.
– A second one (2nd column in Table 3) corresponding to a thick
PMMA sample thermal degradation. During this second stage,
a swelling phenomenon of the PMMA sample occurred and all
exhaust gas amounts and MLR continued increasing (except
for the O2 concentration, which decreased), but more slowly
than previously.
– A third one (3rd column in Table 3) corresponding to a thin
PMMA sample thermal degradation. During this stage, the
swelling phenomenon ended, and PMMA matrix surface crack-
ing occurred. Thus, O2 consumption and effluent production,
as well as the MLR value, reach an optimum value, which
corresponds to the main peak (maximum for exhaust gases
and minimum for oxygen) observed in Fig. 7.
– A fourth one (4th column in Table 3) corresponding to the
oxidation of the remaining amount of the PMMA sample up to
the end of the degradation process (end of the ignition). During
this time range, small CO, CO2 and other gas production
(exhaust product concentrations and MLR values decrease)
and small O2 consumption (oxygen concentration increases up
to the initial value) were observed. At the end of this step, no
residue was found in the sample holder.
6. Conclusion
This study has dealt with the experimental characterization of
thermal degradation and the combustion of a non-fire-retarded
black PMMA. Experiments were carried out using a CC device
under piloted ignition in order to characterize the external
heat flux influence on the degradation process and on gaseous
emissions. The theoretical thermal properties of PMMA degrada-
tion have been calculated. In addition, the exhaust gas analysis
was performed using an FTIR spectrometer and a HORIBA gas
analyzer for heat fluxes ranging from 10 to 60 kW/m2 (with an
experimental CHF equal to 11 kW m  2). The gaseous species
with the main concentrations and main emission yields were

Table 7
Atomic balance between the solid (source) and the exhaust gas (emissions) measured for the 11 irradiance levels studied.

External PMMA mass (g) Initial atomic mass (g) Atomic balance in exhaust gases (g)
heat flux (kW m  2)
C (from PMMA) H (from PMMA) C (from CO and CO2) H (from H2O)

11 168.7 72.5 99.7 7 1.5 13.3 7 0.2 94.1 718.8 13.5 7 4.5
12 171.6 101.4 13.6 93.1 718.6 14.5 7 4.8
15 171.6 72.5 101.4 7 1.5 13.6 7 0.2 100.1 720.0 14.3 7 4.7
20 169.2 73.6 100.07 2.1 13.4 7 0.3 100.7 720.1 13.1 7 4.3
25 173.3 72.5 102.4 7 1.5 13.7 7 0.2 98.3 719.7 12.6 7 4.2
30 167.5 72.6 99.07 1.5 13.2 7 0.2 99.1 719.8 11.8 7 3.9
35 168.0 72.1 99.3 7 1.2 13.3 7 0.2 100.4 720.1 12.0 7 3.9
40 168.2 71.1 99.4 7 0.7 13.3 7 0.1 101.6 720.3 10.9 7 3.6
45 170.4 72.6 100.77 1.5 13.5 7 0.2 103.4 720.7 12.3 7 4.1
50 171.6 73.0 101.4 7 1.8 13.6 7 0.2 104.2 720.8 11.6 7 3.8
55 168.8 72.5 99.8 7 1.5 13.3 7 0.2 101.8 720.4 11.5 7 3.8
60 168.7 72.5 99.7 7 1.5 13.3 7 0.2 102.6 720.5 11.0 7 3.6
Mean 169.6 72.9 100.47 1.5 13.4 7 0.2 99.9 720.0 12.4 7 4.1
460 J. Luche et al. / Fire Safety Journal 46 (2011) 451–461
CO2, CO, H2O, NO and O2, regardless of the irradiance level
studied. The results have shown that emission yields presented
quasi-constant values (measurement and calculation uncertain-
ties taken into account) and were slightly influenced by an
external heat flux increase.
The main product evolutions have been correlated to the
evolutions of the HRR and the SMLR. From the HRR and SMLR,
EHC  24.5 kJ g  1 was computed for each irradiance level. Since
the experiments were carried out in an atmospheric area without
external ventilation, the oxygen supplied to the flame was only
piloted by convection. Then, oxidative reactions were mainly
piloted by flame temperature. As expected, the results obtained
confirm the influence of irradiance levels on the degradation of
the PMMA sample (i.e. on SMLR, HRR and product amounts in the
gaseous phase).
Using Thermogravimetric Analysis or a Tubular Furnace,
where the reactor temperature was increased at a given heating
rate, some previous studies [23,24,50–56] have shown that the
non-charring black PMMA polymer was thermally degraded
according to the following four-step reaction mechanism (where
the term ‘‘gas’’ represents CO, CO2, H2O):
– Depolymerization of PMMA to form MMA-derived monomers
[23,24,50–56] by pyrolysis or oxidation reactions,
Ox:=Py:
PMMA!MMA-derived compoundsþ Gas
– Oxidation of the MMA-derived compounds and their trans-
formations into oxygenated compounds (alcohol, carboxylic
acid, etc.) [23,24,47–53] inside the solid matrix,
O2
MMAderived compounds!Tar=Oxygenated compounds þ Gas
– Oxidation of the oxygenated compounds to form exhaust
gases and small gaseous compounds (formaldehyde, metha-
nol, acetone, acetylene, etc.),
O2
Tar=Oxygenated compounds!Small gaseous compoundsþ Gas
– Small gaseous compound oxidation into gas,
O2
Small gaseous compounds!Gas
This mechanism probably takes place during the entire PMMA
thermal degradation process, and the four steps occur continu-
ously on the whole duration of the CC experiments as soon as
ignition starts. Using numerical simulation, the next step of this
work will be to calculate the Arrhenius parameters of each
reaction by using a parameter optimization method (e.g. genetic
algorithm [57–59]) to demonstrate the validity of this PMMA
thermal degradation mechanism in CC experiments under well-
ventilated air atmospheres.
Acknowledgments
The authors are grateful for the financial support of the French
MAIF foundation (‘‘Fondation MAIF’’) and the COMPFEU program
to this work.
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